CN114751998A - Modified guar gum and preparation method thereof - Google Patents
Modified guar gum and preparation method thereof Download PDFInfo
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- CN114751998A CN114751998A CN202210445747.2A CN202210445747A CN114751998A CN 114751998 A CN114751998 A CN 114751998A CN 202210445747 A CN202210445747 A CN 202210445747A CN 114751998 A CN114751998 A CN 114751998A
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Abstract
The invention relates to modified guar gum and a preparation method thereof. The preparation method comprises the following specific steps: adding sodium diphenylamine sulfonate, water and p-chloromethyl benzoic acid into a reactor in sequence, heating to 70-80 ℃ while stirring, and maintaining the pH of an aqueous solution of sodium hydroxide to 9-10; adding concentrated hydrochloric acid to adjust pH, cooling to below 10 deg.C, separating out solid, and filtering to obtain white crystal; adding the crystal into water, and adjusting the pH value to 9-10 by using a sodium hydroxide aqueous solution; adding epoxy chloropropane while stirring, and heating to 50-60 ℃ to obtain an intermediate solution; adding guar gum and sodium hydroxide aqueous solution into another reactor, reacting for 60-120min, adding the intermediate solution, heating for reaction, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding ethanol, precipitating powdery solid, filtering, and drying to obtain the product modified guar gum. The modified guar gum has the advantages of high apparent viscosity, anti-swelling effect on clay, strong antibacterial capability and the like.
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, relates to a polymer for fracturing and a preparation method thereof, and particularly relates to modified guar gum and a preparation method thereof.
Background
Guar gum is a high molecular water soluble colloid separated from a guar seed of Indian, Pakistan, etc., is a natural galactomannan, which takes mannan as a main chain and single galactopyranose as a side chain, and is connected with the main chain by a (1-6) bond. The fact that galactose is randomly distributed in the backbone, but in groups of two or three, this substantially linear and branched structure determines the good water solubility of guar, and the formation of stable aqueous solutions of high viscosity at lower concentrations, as seen throughout the molecule.
At present, most oil fields enter the middle and later stages of development, most of newly-discovered reservoirs are low in permeability, the reservoirs are well developed only after being transformed through fracturing acidification, and the fracturing effect depends on the performance of fracturing fluid to a great extent. In recent years, hydroxypropyl guar gum is widely used as a thickening agent of oil field fracturing fluid, guar gum molecules contain a large amount of hydroxyl groups, most of the hydroxyl groups are positioned in the molecules, and the hydroxyl groups form intramolecular self-crosslinking through strong intermolecular force, so that the guar gum is difficult to hydrate well. Natural guar gum has certain defects in the aspects of water-soluble speed, insoluble content, solution transparency, viscosity stability and the like, so that the application of the natural guar gum is limited.
Therefore, the natural guar gum is subjected to chemical or physical modification, so that the performance of the guar gum can be effectively improved, and the application range is further enlarged.
CN102827300A discloses a preparation method and application of a hydrophobic modified guar gum, comprising the following steps: suspending guar gum in ionic liquid, adding an alkaline catalyst, and alkalizing at 10-40 ℃; gradually heating under the protection of nitrogen, slowly dripping a modifier, and heating to 30-80 ℃ to perform modification reaction; and after the reaction is finished, adding organic acid to adjust the pH value to 5-7, soaking and washing with ethanol, filtering, and drying a filter cake in vacuum to obtain the hydrophobic modified guar gum. According to the invention, the hydrophobic alkyl long chain is introduced on the guar gum hydroxyl, the terminal group is carboxylic acid group, the water-soluble speed of the guar gum is improved, the macromolecular quality characteristic of the guar gum is protected to the maximum extent, and the guar gum is endowed with hydrophobic performance. Compared with other modified guar gums, the hydrophobic guar gum has large molecular weight and good affinity with cellulose, increases the molecular binding force of the cellulose-guar gum, thereby improving the paper strength, and can be used as a reinforcing agent and a surface sizing agent to be applied to the chemical process of a papermaking wet end. However, the modified guar gum only adds hydrophobic groups into the molecule, so that the dissolution speed is slow, and the modified guar gum is not favorable for quick preparation and use in the field.
CN 109569541A discloses a modified guar gum, which is a guar gum containing a grafted chain, wherein the grafted chain is of a structure shown in a formula I; the grafting chain is connected with the modified guar gum through an ether bond; the oxygen in the ether linkage is provided by hydroxyl groups on the guar gum; the mass percentage content of the grafting chain in the modified guar gum is 69.5-80.3%; wherein n is1R is-NH (CH) 1-62)2NH2、-NH(CH2)2NH(CH2)2NH2or-NH (CH)2)2NH(CH2)2NH(CH2)2NH(CH2)2NH2. The modified guar gum provided by the invention contains a large amount of nitrogen atoms with lone pair electrons, can be more fully chelated with heavy metal ions, and has a saturated adsorption capacity of 32.7-141.5 mg g for heavy metal nickel ions-1. However, according to molecular structure analysis, the modified guar gum has no bacteriostatic function and is easy to be attacked by microorganisms, so that the modified guar gum needs to be prepared immediately after being used on site.
Disclosure of Invention
The invention provides a modified guar gum and a preparation method thereof aiming at the defects of the prior art. The guar gum has the advantages of high apparent viscosity, anti-swelling effect on clay, strong antibacterial capability and the like.
One of the purposes of the invention discloses a modified guar gum, the molecular structural formula of which is as follows:
The invention also discloses a synthesis method of the modified guar gum, which comprises the following specific steps:
(1) adding sodium diphenylamine sulfonate, water and p-chloromethyl benzoic acid into a reactor in sequence, heating to 70-80 ℃ while stirring, and carrying out heat preservation reaction, wherein the pH value is maintained at 9-10 by using a sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, simultaneously cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal;
(2) adding the crystal into water, and adjusting the pH value to 9-10 by using a sodium hydroxide aqueous solution; adding epoxy chloropropane while stirring, heating to 50-60 ℃ after the addition, and carrying out heat preservation reaction to obtain an intermediate solution;
(3) adding guar gum and sodium hydroxide aqueous solution into another reactor, stirring and reacting for 60-120min, adding the intermediate solution, heating and reacting, adjusting the pH to 6-8 with 30 wt% acetic acid, adding ethanol, precipitating powdery solid, filtering, and drying to obtain the product modified guar gum.
Preferably, in the step (1), the weight ratio of the diphenylamine sodium sulfonate to the water to the p-chloromethylbenzoic acid is 1:2-4:0.6-0.66, and more preferably 1:2.5-3.5: 0.62-0.64.
Preferably, in step (1), the concentration of the aqueous sodium hydroxide solution is 10 to 25 wt%, more preferably 15 to 20 wt%.
Preferably, in the step (1), the reaction time of the heat preservation is 4-10h, and more preferably 6-8 h.
Preferably, in the step (2), the weight ratio of the water to the epichlorohydrin to the sodium diphenylamine sulfonate is 2-4: 0.31-0.37:1, more preferably 2.5-3.5:0.33-0.35: 1.
Preferably, in step (2), the concentration of the aqueous sodium hydroxide solution is 10 to 25 wt%, more preferably 15 to 20 wt%.
Preferably, in the step (2), the incubation reaction time is 2-6h, and more preferably 3-5 h.
Preferably, in the step (3), the weight ratio of the guar gum, the sodium hydroxide, the ethanol and the sodium diphenylamine sulfonate is 1.2-1.8:0.04-0.07: 1-3: 1, more preferably 1.4-1.6:0.05-0.06: 1.5-2.5: 1.
preferably, in step (3), the concentration of the aqueous sodium hydroxide solution is 5 to 15 wt%, more preferably 8 to 12 wt%.
Preferably, in the step (3), the temperature rise is 50-80 ℃, the reaction time is 5-10h, more preferably, the temperature is 60-70 ℃, and the reaction time is 7-8 h.
The reaction equation for the synthesis of the modified guar of the invention is as follows:
sulfonic acid, carboxylic acid anions and quaternary ammonium cations are simultaneously introduced into the modified guar gum molecule, and the characteristics of the zwitterionic polymer and the hydrophobic association polymer are combined, so that the space network structure of the guar gum aqueous solution becomes denser, and the amphoteric guar gum is ensured to have higher surface viscosity. The introduction of sulfonic acid and carboxylic acid anions increases the temperature resistance and salt tolerance of the composite material. After guar gum enters a stratum, quaternary ammonium cations in molecules enable negative charges on the surface of clay to be adsorbed and neutralized, the electrostatic attraction is increased, the repulsion between crystal layers is reduced, and the anti-swelling effect is achieved; benzene rings in the molecules change the surface of the adsorbed clay from hydrophilic to lipophilic, and swelling is inhibited by preventing water molecules from contacting the clay to wet the clay. In addition, the quaternary ammonium cation has stronger bactericidal capacity, so the prepared fracturing fluid has stronger antibacterial capacity.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the modified guar gum has the characteristic of high apparent viscosity, wherein the apparent viscosity is more than 350mPa.s and can reach more than 400mPa.s at most;
(2) the modified guar gum has the effect of a clay stabilizer, and the anti-swelling rate is more than 95%;
(3) the modified guar gum disclosed by the invention has stronger antibacterial performance, and the viscosity retention rate can reach more than 92% after 120 hours.
Detailed Description
Example 1
(1) Sequentially adding 100g of diphenylamine sodium sulfonate, 200g of water and 60g of p-chloromethyl benzoic acid into a reactor, heating to 70 ℃ while stirring, and carrying out heat preservation reaction for 4 hours, wherein the pH value is maintained to be 9-10 by using a 10 wt% sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) Adding the crystal into 200g of water, and adjusting the pH value to 9-10 by using 10 wt% of sodium hydroxide solution; adding 31g of epoxy chloropropane while stirring, heating to 50 ℃ after the completion of the reaction, and carrying out heat preservation reaction for 2 hours to obtain an intermediate solution.
(3) Adding 120G of guar gum and 80G of 5 wt% sodium hydroxide solution into another reactor, stirring for reaction for 60min, adding the intermediate solution, heating to 50 ℃ for reaction, keeping the temperature for 10h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 100G of ethanol, precipitating powdery solid, filtering and drying to obtain a product, namely modified guar gum G 1。
Example 2
(1) Sequentially adding 100g of diphenylamine sodium sulfonate, 400g of water and 62g of p-chloromethyl benzoic acid into a reactor, heating to 73 ℃ while stirring, and carrying out heat preservation reaction for 9 hours, wherein the pH value is maintained to be 9-10 by using a 25 wt% sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The above crystals were added to 380g of water, and the pH was adjusted to 9-10 with 25 wt% sodium hydroxide solution. Adding 37g of epoxy chloropropane while stirring, heating to 52 ℃ after the completion of the reaction, and carrying out heat preservation reaction for 5 hours to obtain an intermediate solution.
(3) Adding 170G of guar gum and 46.67G of 15 wt% sodium hydroxide solution into another reactor, stirring for reaction for 80min, adding the intermediate solution, heating to 80 ℃ for reaction, keeping the temperature for 5h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 271.3G of ethanol, precipitating a powdery solid, filtering and drying to obtain a product, namely modified guar gum G2。
Example 3
(1) Sequentially adding 100g of diphenylamine sodium sulfonate, 250g of water and 61g of p-chloromethyl benzoic acid into a reactor, heating to 72 ℃ while stirring, and carrying out heat preservation reaction for 5.5 hours, wherein the pH value is maintained to be 9-10 by using a 13 wt% sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The crystals were added to 238g of water and the pH was adjusted to 9-10 with 15% by weight sodium hydroxide solution. Adding 32.4g of epoxy chloropropane while stirring, heating to 54 ℃ after the completion, and keeping the temperature for reaction for 3 hours to obtain an intermediate solution.
(3) Adding 180G of guar gum and 66.2G of 7.4 wt% sodium hydroxide solution into another reactor, stirring for reaction for 70min, adding the intermediate solution, heating to 61 ℃ for reaction, keeping the temperature for 8.8h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 120.6G of ethanol, precipitating powdery solid, filtering and drying to obtain the product modified guar gum G3。
Example 4
(1) 100g of sodium diphenylamine sulfonate, 350g of water and 64g of p-chloromethyl benzoic acid are sequentially added into a reactor, the temperature is raised to 74 ℃ while stirring, the temperature is kept for 10 hours of reaction, and the pH value is maintained to be 9-10 by using 21.5 weight percent of sodium hydroxide aqueous solution in the reaction period. Adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The crystals were added to 400g of water and the pH was adjusted to 9-10 with 21% by weight sodium hydroxide solution. Adding 34.9g of epoxy chloropropane while stirring, heating to 55 ℃ after the completion of the reaction, and carrying out heat preservation reaction for 5 hours to obtain an intermediate solution.
(3) Adding 168G of guar gum and 48.4G of 12.4 wt% sodium hydroxide solution into another reactor, stirring for reaction for 85min, adding the intermediate solution, heating to 71 ℃ for reaction, keeping the temperature for 6.1h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 180G of ethanol, precipitating a powdery solid, filtering and drying to obtain a product, namely modified guar gum G 4。
Example 5
(1) Sequentially adding 100g of diphenylamine sodium sulfonate, 250g of water and 66g of p-chloromethyl benzoic acid into a reactor, heating to 76 ℃ while stirring, and carrying out heat preservation reaction for 7 hours, wherein the pH value is maintained to be 9-10 by using a 17 wt% sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The crystals were added to 280g of water and the pH was adjusted to 9-10 with 17% by weight sodium hydroxide solution. Adding 33.7g of epoxy chloropropane while stirring, heating to 56 ℃ after the completion of the reaction, and carrying out heat preservation reaction for 6 hours to obtain an intermediate solution.
(3) Adding 141G of guar gum and 60.7G of 8.4 wt% sodium hydroxide solution into another reactor, stirring for reaction for 90min, adding the intermediate solution, heating to 56 ℃ for reaction, keeping the temperature for 7.9h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 220G of ethanol, precipitating a powdery solid, filtering and drying to obtain a product, namely modified guar gum G5。
Example 6
(1) Sequentially adding 100g of diphenylamine sodium sulfonate, 300g of water and 62g of p-chloromethyl benzoic acid into a reactor, heating to 80 ℃ while stirring, and carrying out heat preservation reaction for 10 hours, wherein the pH value is maintained to be 9-10 by using a 20 wt% sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The crystals were added to 330g of water and the pH was adjusted to 9-10 with 20% by weight sodium hydroxide solution. Adding 34.5g of epoxy chloropropane while stirring, heating to 53 ℃ after the completion of the reaction, and carrying out heat preservation reaction for 4.4 hours to obtain an intermediate solution.
(3) Adding 158G of guar gum and 44.2G of 11.8 wt% sodium hydroxide solution into another reactor, stirring for reaction for 105min, adding the intermediate solution, heating to 68 ℃ for reaction, keeping the temperature for 7.3h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 200G of ethanol, precipitating a powdery solid, filtering and drying to obtain a product, namely modified guar gum G6。
Example 7
(1) Sequentially adding 100g of sodium diphenylamine sulfonate, 280g of water and 63g of p-chloromethyl benzoic acid into a reactor, heating to 78 ℃ while stirring, and carrying out heat preservation reaction for 8 hours, wherein the pH value is maintained to be 9-10 by using 18 wt% of sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The crystals were added to 300g of water and the pH was adjusted to 9-10 with 18% by weight sodium hydroxide solution. Adding 34.1g of epoxy chloropropane while stirring, heating to 60 ℃ after the completion, and keeping the temperature for reaction for 3.8h to obtain an intermediate solution.
(3) Adding 149G of guar gum and 54.7G of 9.5 wt% sodium hydroxide solution into another reactor, stirring for reaction for 110min, adding the intermediate solution, heating to 55 ℃ for reaction, keeping the temperature for 6h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 300G of ethanol, precipitating powdery solid, filtering and drying to obtain a product, namely modified guar gum G 7。
Example 8
(1) Sequentially adding 100g of sodium diphenylamine sulfonate, 320g of water and 66g of p-chloromethyl benzoic acid into a reactor, heating to 72 ℃ while stirring, and carrying out heat preservation reaction for 9 hours, wherein the pH value is maintained to be 9-10 by using a 19.2 wt% sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal.
(2) The crystals were added to 310g of water and the pH was adjusted to 9-10 with 19% by weight sodium hydroxide solution. Adding 34.2g of epoxy chloropropane while stirring, heating to 53 ℃ after the completion of the reaction, and carrying out heat preservation reaction for 4.1h to obtain an intermediate solution.
(3) Adding 150G of guar gum and 52.4G of 10.5 wt% sodium hydroxide solution into another reactor, stirring for reaction for 120min, adding the intermediate solution, heating to 64 ℃ for reaction, keeping the temperature for 7.6h, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding 180G of ethanol, precipitating powdery solid, filtering and drying to obtain the product modified guar gum G8。
Test example 1 measurement of apparent viscosity
The evaluation method refers to SY/T5764-2007 general technical requirements of vegetable gum for fracturing
Weighing 500ml of distilled water in a mixing and adjusting device, starting at low speed, slowly adding 3.00g of rubber powder, and adjusting the voltage to
Stirring for 5min, pouring the rubber powder solution into a beaker, covering, placing in a water bath at 30 ℃, keeping the temperature for 4h, and testing the apparent viscosity. The results of the apparent viscosity test of the modified guar gum are shown in table 1.
Test example 2 evaluation of anti-swelling Rate capability
The evaluation method refers to SY/T5971-2016 & lt & ltmethod for evaluating performances of clay stabilizers for oil and gas field fracturing acidizing and water injection & gt, and the centrifugal method is used for testing the anti-swelling rate.
0.5g of modified guar gum is taken, 100g of distilled water is added, and the mixture is shaken up.
Weighing 0.50g of sodium bentonite, putting into a 10mL centrifuge tube, adding 10mL of guar gum solution, fully shaking, standing at room temperature for 2h, putting into a centrifuge, centrifugally separating at the rotating speed of 1500r/min for 15min, and reading out the volume V of the expanded sodium bentonite1。
Volume V of swelled sodium bentonite with distilled water instead of clay stabilizer solution2。
Volume V of sodium bentonite after swelling by using kerosene instead of clay stabilizer solution0。
Method for calculating anti-swelling rate
The results of the swelling resistance test of the modified guar gum are shown in table 1.
Test example 3 test of antibacterial ability
The evaluation method refers to Q/SH 10250784-2011 technical conditions of bactericide for fracturing
Preparing a base liquid: 1000ml of tap water is measured and poured into the Wuyi mixing and adjusting device, and the rotating speed of the Wuyi mixing and adjusting device is adjusted until the top end of a paddle center shaft of the mixing and adjusting device can be seen in a vortex formed by liquid. Then slowly adding 5g of modified guar gum to form a uniform solution, stopping stirring, and standing in an electric heating constant temperature incubator at 30 ℃ for constant temperature.
Preparation of jelly: weighing 70ml of the base solution, pouring the base solution into a 100ml beaker, sequentially adding 0.35ml of high-temperature fracturing stabilizer and 0.30ml of liquid sodium hydroxide under the stirring of a glass rod, uniformly stirring, and then adding 0.35ml of cross-linking agent while stirring until uniform gel capable of being hung is formed.
And (3) viscosity measurement: the base fluids with constant temperature of 4h and 120h are respectively prepared into jelly glue, then the jelly glue is put into an RT20 type rheometer, and the temperature resistance and the shearing resistance of the fracturing fluid are measured according to 6.6 in SY/T5107-2005 water-based fracturing fluid performance evaluation method. Setting the temperature to 120 ℃, setting the rotorAt a shear rate of 170s-1And (5) shearing for 90min, and taking the average value of the apparent viscosities corresponding to the last 10min of shearing as the apparent viscosity of the jelly.
In the formula:
r-antibacterial ability,%;
eta 1-apparent viscosity of the jelly at constant temperature of 4h, wherein the unit is mPa & s;
eta 2-apparent viscosity of the base solution in mPas at constant temperature for 120 h.
The results of the modified guar gum antibacterial ability test are shown in table 1.
TABLE 1 apparent viscosity, anti-swelling rate, antibacterial ability test results of modified guar gum
| Guar gum | Apparent viscosity, mPas | Anti-swelling rate of% | Antibacterial ability,% |
| G1 | 354 | 95.8 | 92.2 |
| G2 | 367 | 95.6 | 93.1 |
| G3 | 369 | 95.9 | 93.5 |
| G4 | 361 | 96.8 | 94.0 |
| G5 | 382 | 96.7 | 93.2 |
| G6 | 376 | 96.4 | 94.1 |
| G7 | 395 | 96.8 | 93.6 |
| G8 | 412 | 97.5 | 95.2 |
| Before transformation | 181 | 36.5 | 36.8 |
As can be seen from table 1:
(1) The apparent viscosity of the modified guar gum is more than 350 mPas, wherein G8The highest apparent viscosity reaches 412 mPas, the apparent viscosity of the guar gum before reconstruction is 181 mPas, and the apparent viscosity of the modified guar gum is obviously higher than that of the guar gum before reconstruction, and is higher than 190 mPas on average. Compared with the existing product, the modified guar gum has good apparent viscosity performance.
(2) The anti-swelling rate of the modified guar gum is more than 95 percent, wherein G8The highest content of the modified guar gum is 95.2 percent, the anti-swelling rate of the modified guar gum is 36.5 percent, and the anti-swelling rate of the modified guar gum is obviously higher than that of the modified guar gum by more than 60 percent on average. Compared with the existing product, the modified guar gum has good anti-swelling effect.
(3) The antibacterial capacity of the modified guar gum is more than 92 percent, wherein G1Minimum 92.2%, G8The highest is 95.2%, the antibacterial capacity of the modified guar gum is 36.8%, and the antibacterial capacity of the modified guar gum is obviously higher than that of the modified guar gum, and is averagely higher than 56 percentage points. Compared with the existing product, the modified guar gum has stronger antibacterial ability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The preparation method of the modified guar gum is characterized by comprising the following specific steps:
(1) sequentially adding sodium diphenylamine sulfonate, water and p-chloromethyl benzoic acid into a reactor, heating to 70-80 ℃ while stirring, and carrying out heat preservation reaction, wherein the pH value is maintained at 9-10 by using a sodium hydroxide aqueous solution; adding concentrated hydrochloric acid, adjusting pH to 2, simultaneously cooling to below 10 deg.C, precipitating solid, and filtering to obtain white crystal;
(2) adding the crystal into water, and adjusting the pH value to 9-10 by using a sodium hydroxide aqueous solution; adding epoxy chloropropane while stirring, heating to 50-60 ℃ after the completion of the reaction, and carrying out heat preservation reaction to obtain an intermediate solution;
(3) adding guar gum and sodium hydroxide aqueous solution into another reactor, stirring and reacting for 60-120min, adding the intermediate solution, heating and reacting, adjusting the pH value to 6-8 by using 30 wt% acetic acid, adding ethanol, precipitating powdery solid, filtering and drying to obtain the product modified guar gum.
2. The method according to claim 1, wherein in the step (1), the weight ratio of sodium diphenylamine sulfonate, water and p-chloromethyl benzoic acid is 1:2-4: 0.6-0.66.
3. The method according to claim 2, wherein in the step (1), the weight ratio of sodium diphenylamine sulfonate, water and p-chloromethyl benzoic acid is 1:2.5-3.5: 0.62-0.64.
4. The method according to claim 1, wherein in the step (1), the incubation reaction time is 4 to 10 hours.
5. The preparation method according to claim 1, wherein in the step (2), the weight ratio of the water to the epichlorohydrin to the sodium diphenylamine sulfonate is 2-4: 0.31-0.37:1.
6. The preparation method according to claim 5, wherein in the step (2), the weight ratio of the water to the epichlorohydrin to the sodium diphenylamine sulfonate is 2.5-3.5:0.33-0.35: 1.
7. The method according to claim 1, wherein in the step (2), the incubation reaction time is 2 to 6 hours.
8. The preparation method according to claim 1, wherein in the step (3), the weight ratio of the guar gum, the sodium hydroxide, the ethanol and the sodium diphenylamine sulfonate is 1.2-1.8:0.04-0.07: 1-3: 1.
9. the method according to claim 1, wherein in the step (3), the temperature is raised to 50-80 ℃ and the reaction time is 5-10 hours.
10. Modified guar gum obtained by the process according to any of claims 1 to 9, characterized in that it has the following molecular formula:
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| CN117088993A (en) * | 2023-10-18 | 2023-11-21 | 东营市宝泽能源科技有限公司 | Guar gum for oilfield fracturing and preparation method thereof |
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